Insecticidal pyridine compounds

ABSTRACT

The invention disclosed in this document is related to the field of pesticides and their use in controlling pests. Novel pyridine compounds for use in controlling pests are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 12/799,478 filed 26 Apr. 2009, which claims priority to U.S.Provisional Patent Application No. 61/172,958 filed 27 Apr. 2009. Thecontents of these applications are incorporated herein by reference intheir entirety.

FIELD OF THE INVENTION

The inventions disclosed in this document are related to the field ofpesticides and their use in controlling pests.

BACKGROUND

Pests cause millions of human deaths around the world each year.Furthermore, there are more than ten thousand species of pests thatcause losses in agriculture. These agricultural losses amount tobillions of U.S. dollars each year. Termites cause damage to variousstructures such as homes. These termite damage losses amount to billionsof U.S. dollars each year. As a final note, many stored food pests eatand adulterate stored food. These stored food losses amount to billionsof U.S. dollars each year, but more importantly, deprive people ofneeded food.

There is an acute need for new pesticides. Insects are developingresistance to pesticides in current use. Hundreds of insect species areresistant to one or more pesticides. The development of resistance tosome of the older pesticides, such as DDT, the carbonates, and theorganophosphates, is well known. But resistance has even developed tosome of the newer pesticides. Therefore, a need exists for newpesticides and particularly for pesticides that have new modes ofaction.

SUMMARY

This invention concerns compounds useful for the control of insects,especially useful for the control of aphids and other sucking insects.More specifically, the invention concerns compounds of formula I:

wherein A1, A2, A3, X, Y, Z, T, n, R1, R2, R3, R4, R5, R6 and R7 are asdefined herein.

The invention also provides new processes for preparing compounds offormula I as well as new compositions and methods of use, which will bedescribed in detail hereinafter. Further embodiments, forms, aspects,features, and details of the present invention shall become apparentfrom the descriptions contained herein.

DETAILED DESCRIPTION

The compounds of this application have the following molecularstructure:

wherein

A1, A2, and A3, are each independently C or N, with the proviso that A1and A2 are not simultaneously N;

X and Y are independently C or N;

Z and T are each independently C(R6)₂ (where R6 could be the same ordifferent), C═O, C═NR7, NR7, O, S(O)n′ (n′=0-2);

n=0, 1, 2 and 3 (X, Y, T and Z together form a 3- or 4- or 5- or6-membered heteroaryl or a fully or partially saturated heterocyclicring);

R1 is (provided that A1 is not N) H, CN, CHO, —SCN, NO₂, F, Cl, Br, I,substituted or unsubstituted C1-C4-alkyl, substituted or unsubstitutedhalo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy, substitutedor unsubstituted halo-C1-C4-alkoxy, substituted or unsubstitutedC1-C4-thioalkyl, substituted or unsubstituted halo-C1-C4-thioalkyl,substituted or unsubstituted C3-C7-cycloalkyl, substituted orunsubstituted C2-C4-alkenyl, C2-C4-alkynyl, substituted or unsubstitutedC1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,C1-C4-alkoxy-amino, C1-C4-alkyl-S(O)═NH, substituted or unsubstitutedaryl, substituted or unsubstituted heterocyclyl, wherein thesubstituents are one or more of the following F, Cl, Br, OH, CN, NO₂,CHO, —SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl,halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy,C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy,C1-C4 alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino,C1-C4-alkyl-S(O)═NH, (C1-C4-trialkyl)Si;

R2 is (provided that A2 is not N) H, CN, CHO, —SCN, NO₂, F, Cl, Br, I,substituted or unsubstituted C1-C4-alkyl, substituted or unsubstitutedhalo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy, substitutedor unsubstituted halo-C1-C4-alkoxy, substituted or unsubstitutedC1-C4-thioalkyl, substituted or unsubstituted halo-C1-C4-thioalkyl,substituted or unsubstituted C3-C7-cycloalkyl, substituted orunsubstituted C2-C4-alkenyl, C2-C4-alkynyl, substituted or unsubstitutedC1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,C1-C4-alkoxy-amino, C1-C4-alkyl-S(O)═NH, substituted or unsubstitutedaryl, substituted or unsubstituted heterocyclyl, wherein thesubstituents are one or more of the following F, Cl, Br, OH, CN, NO₂,CHO, —SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl,halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy,C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy,C1-C4 alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino,C1-C4-alkyl-S(O)═NH, (C1-C4-trialkyl)Si;

R3 is CN, NO₂, F, Cl, Br, I, substituted or unsubstitutedhalo-C1-C4-alkyl, or unsubstituted C3-C7-cycloalkyl, substituted orunsubstituted halo-C1-C4-alkoxy, substituted or unsubstitutedhalo-C1-C4-thioalkyl substituted or unsubstituted halo-C2-C4-alkenyl,substituted or unsubstituted five membered heteroaryl, wherein thesubstituents are one or more of the following F, Cl. Br, OH, CN, NO₂,CHO, —SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl,halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy,C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy,C1-C4 alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino,C1-C4-alkyl-S(O)═N;

R4 is (provided that A3 is not N) H, CN, CHO, —SCN, NO₂, F, Cl, Br, I,substituted or unsubstituted C1-C4-alkyl, substituted or unsubstitutedhalo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy, substitutedor unsubstituted halo-C1-C4-alkoxy, substituted or unsubstitutedC1-C4-thioalkyl, substituted or unsubstituted halo-C1-C4-thioalkyl,substituted or unsubstituted C3-C7-cycloalkyl, substituted orunsubstituted C2-C4-alkenyl, C2-C4-alkynyl, substituted or unsubstitutedC1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,C1-C4-alkoxy-amino, C1-C4-alkyl-S(O)═NH, substituted or unsubstitutedaryl, substituted or unsubstituted heterocyclyl, wherein thesubstituents are one or more of the following F, Cl, Br, OH, CN, NO₂,CHO, —SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl,halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy,C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy,C1-C4 alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino,C1-C4-alkyl-S(O)═NH, (C1-C4-trialkyl)Si:

R5 is H, CN, CHO, —SCN. NO₂, F, Cl, Br, I, substituted or unsubstitutedC1-C4-alkyl, substituted or unsubstituted halo-C1-C4-alkyl, substitutedor unsubstituted C1-C4-alkoxy, substituted or unsubstitutedhalo-C1-C4-alkoxy, substituted or unsubstituted C1-C4-thioalkyl,substituted or unsubstituted halo-C1-C4-thioalkyl, substituted orunsubstituted C3-C7-cycloalkyl, substituted or unsubstitutedC2-C4-alkenyl, C2-C4-alkynyl, substituted or unsubstitutedC1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,C1-C4-alkoxy-amino, C1-C4-alkyl-S(O)═NH, substituted or unsubstitutedaryl, substituted or unsubstituted heterocyclyl, wherein thesubstituents are one or more of the following F, Cl, Br, OH, CN, NO₂,CHO, —SCN, S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl,halo-C1-C4-alkyl, C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy,C1-C4-thioalkyl, halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy,C1-C4 alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino,C1-C4-alkyl-S(O)═NH, (C1-C4-trialkyl)Si;

R6 is H, OH, SH, CN, CHO, —SCN, NO₂, F, Cl, Br, I, substituted orunsubstituted C1-C4-alkyl, substituted or unsubstitutedhalo-C1-C4-alkyl, substituted or unsubstituted C1-C4-alkoxy, substitutedor unsubstituted halo-C1-C4-alkoxy, substituted or unsubstitutedC1-C4-thioalkyl, substituted or unsubstituted halo-C1-C4-thioalkyl,substituted or unsubstituted C3-C7-cycloalkyl, substituted orunsubstituted C2-C4-alkenyl, C2-C4-alkynyl, substituted or unsubstitutedC1-C4-acylalkyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,C1-C4-alkyl-S(O)═NH, substituted or unsubstituted aryl, substituted orunsubstituted heterocyclyl, wherein the substituents are one or more ofthe following F, Cl, Br, OH, CN, NO₂, CHO, —SCN, S(O)n-C1-C4-alkyl(where n=0-2), C1-C4-alkyl, halo-C1-C4-alkyl, C1-C4-alkylamine,C1-C4-alkoxy, halo-C1-C4-alkoxy, C1-C4-thioalkyl, halo-C1-C4-thioalkyl,C1-C4-alkylacyl, C1-C4-acyloxy, C1-C4 alkoxycarbonyl,C1-C4-alkoxy-imino, hydroxy-imino, C1-C4-alkyl-S(O)═NH,(C1-C4-trialkyl)Si; and

R7 is H, OH, CN, NH2, CHO, —SCN, NO₂, substituted or unsubstitutedC1-C4-alkyl, substituted or unsubstituted halo-C1-C4-alkyl, substitutedor unsubstituted C1-C4-alkoxy, substituted or unsubstitutedhalo-C1-C4-alkoxy, substituted or unsubstituted C1-C4-alkylamine,substituted or unsubstituted C1-C4-thioalkyl, substituted orunsubstituted halo-C1-C4-thioalkyl, substituted or unsubstitutedC3-C7-cycloalkyl, substituted or unsubstituted C2-C4-alkenyl,substituted or unsubstituted C1-C4-acylalkyl, C1-C4-acyloxy, C1-C4alkoxycarbonyl, C1-C4-alkyl-S(O)═NH, substituted or unsubstituted aryl,substituted or unsubstituted heterocyclyl, wherein the substituents areone or more of the following F, Cl, Br, OH, CN, NO₂, CHO, —SCN,S(O)n-C1-C4-alkyl (where n=0-2), C1-C4-alkyl, halo-C1-C4-alkyl,C1-C4-alkylamine, C1-C4-alkoxy, halo-C1-C4-alkoxy, C1-C4-thioalkyl,halo-C1-C4-thioalkyl, C1-C4-alkylacyl, C1-C4-acyloxy, C1-C4alkoxycarbonyl, C1-C4-alkoxy-imino, hydroxy-imino, C1-C4-alkyl-S(O)═NH,(C1-C4-trialkyl)Si.

Substituents (Non-Exhaustive List)

The examples given for the substituents are (except for halo)non-exhaustive and must not be construed as limiting the inventiondisclosed in this document.

“alkenyl” means an acyclic, unsaturated (at least one carbon-carbondouble bond), branched or unbranched, substituent consisting of carbonand hydrogen, for example, vinyl, allyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, and decenyl.

“alkoxy” means an alkyl further consisting of a carbon-oxygen singlebond, for example, methoxy, ethoxy, propoxy, isopropoxy, 1-butoxy,2-butoxy, isobutoxy, tert-butoxy, pentoxy, 2-methylbutoxy,1,1-dimethylpropoxy, hexoxy, heptoxy, octoxy, nonoxy, and decoxy.

“alkyl” means an acyclic, saturated, branched or unbranched, substituentconsisting of carbon and hydrogen, for example, methyl, ethyl, propyl,isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl,2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, anddecyl.

“alkynyl” means an acyclic, unsaturated (at least one carbon-carbontriple bond, and any double bonds), branched or unbranched, substituentconsisting of carbon and hydrogen, for example, ethynyl, propargyl,butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, and decynyl.

“aryl” means a cyclic, aromatic substituent consisting of hydrogen andcarbon, for example, phenyl, naphthyl, and biphenylyl.

“cycloalkyl” means a monocyclic or polycyclic, saturated substituentconsisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl,bicyclo[2.2.2]octyl, and decahydronaphthyl.

“halo” means fluoro, chloro, bromo, and iodo.

“haloalkyl” means an alkyl further consisting of, from one to themaximum possible number of, identical or different, halos, for example,fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoromethyl,2-fluoroethyl, 2,2,2-trifluoroethyl, chloromethyl, trichloromethyl, and1,1,2,2-tetrafluoroethyl.

“heterocyclyl” means a cyclic substituent that may be fully saturated,partially unsaturated, or fully unsaturated, where the cyclic structurecontains at least one carbon and at least one heteroatom, where saidheteroatom is nitrogen, sulfur, or oxygen, for example, benzofuranyl,benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl,isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, 1,3,4 oxadiazolyl,oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl,pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl,quinoxalinyl, 1,2,3,4-tetrazolyl, thiazolinyl, thiazolyl, thienyl,1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, 1,2,3-triazolyl, and1,2,4-triazolyl.

Synthesis Schemes (Non-Exhaustive List)

Compounds of the formula (I) can be prepared according to the followingmethods.

Method 1

Compounds of the formula (I) can be prepared by treating compounds ofthe formula (II), where LG is a halogen (F, Cl, Br, I) or a sulfone orother leaving group and R1, R2, R3, R4, A1, A2 and A3 are as definedabove, and compounds of the formula (III), where R5, X, Y, Z and T areas defined above, in an aprotic or protic solvent in the presence of astoicheometric or catalytic amount of a base at a temperature between−20 and 250° C. (heating under conventional or in a microwave reactor)and at a pressure (0-300 psi) (Scheme 1). Suitable solvents, include,but are not limited to, water, tetrahydrofuran, 1,4-dioxane,dimethylformamide, dimethylsulfoxide, acetonitrile, chloroform,methylene chloride, and mixtures thereof. In some cases the reaction canbe carried out in the presence of excess amine (III) with no solvents.Suitable bases include, but not limited to, metal alkoxides, tertiaryamines and metal hydrides,

Method 2

Compounds of the formula (I) can be prepared by treating compounds ofthe formula (IV), where LG is Cl, Br, I, dialkylborinate, orC1-C4-trialkyl stannane and R1, R2, R3, R4, A1, A2 and A3 are as definedabove, and compounds of the formula (III), where X, Y, T, Z, n and R5are as defined above, in an aprotic or protic solvent in the presence ofa stoicheometric or catalytic amount of a base, a metal- (for example,Pd, Cu, Ni) catalyst and a suitable ligands such as trialkyl phosphinesor arsines, at a temperature between −20 and 250° C. (heating underconventional or in a microwave reactor) at a pressure between 0-300 psi(Scheme [2]). Suitable solvents include, but are not limited to, water,tetrahydrofuran, 1,4-dioxane, dimethylformamide, dimethylsulfoxide,acetonitrile, chloroform, 1,2-dichloroethane, methylene chloride, andmixtures thereof. Suitable bases include, but not limited to, metalalkoxides, tertiary amines and metal hydrides.

Method 3

Compounds of the formula (I) can be prepared by treating compounds ofthe formula (V), where Y═N and R1, R2, R3, R4, X, T, Z, n, A1, A2 and A3are as defined above, and compounds of the formula (VI), where R5 is asdefined above and LG is Cl, Br, I, a sulfone or other leaving group, inan protic or aprotic solvent in the presence of a stoicheometric orcatalytic amount of a base at a suitable temperature between −20 and250° C. (heating conventionally or in a microwave reactor) and at apressure between 0-300 psi (Scheme [3]). Suitable solvents include, butare not limited to, water, tetrahydrofuran, 1,4-dioxane,dimethylformamide, dimethylsulfoxide, acetonitrile, chloroform,methylene chloride, and mixtures thereof. In some cases the reaction canbe carried out in the presence of excess amine (VI) with no solvents.Suitable bases include, but not limited to, metal alkoxides, tertiaryamines and metal hydrides,

Method 4

Compounds of the formula (I) can be prepared by treating compounds ofthe formula (V), where Y═N and R1, R2, R3, R4, X, T, Z, n, A1, A2 and A3are as defined above and compounds of the formula (VII), where LG is Cl,Br, I, dialkylborinate, or C1-C4-trialkyl stannane and R5 is as definedabove, in an aprotic or protic solvent in the presence of astoicheometric or catalytic amount of a base, a metal- (for example, Pd,Cu, Ni) catalyst and a suitable ligands such as trialkyl phosphines orarsenes, at a temperature between −20 and 250° C. (eating underconventional or in a microwave reactor) at a pressure between 0-300 psi(Scheme [4]). Suitable solvents include, but are not limited to, water,tetrahydrofuran, 1,4-dioxane, dimethylformamide, dimethylsulfoxide,acetonitrile, chloroform, 1,2-dichloroethane, methylene chloride, andmixtures thereof.

Suitable bases include, but not limited to, metal alkoxides, tertiaryamines and metal hydrides.

Method 5

Compounds of the formula (I) can be prepared by treatment of thecompounds of the formula (VIII), where R1, R2, R3, R4, X, Z, n, A1, A2,and A3 are as defined above, and compounds of the formula (IX), where Mis H or C, in an aprotic solvent in the presence of an acid catalystunder dehydrating conditions such as in a Dean-Stark set-up or additivessuch as molecular sieves, anhydrous magnesium sulfate (Scheme [5]).Suitable acid catalysts include, but are not limited to, hydrochloricacid, sulfonic acids and sulfuric acid. Preferred solvents include butare not limited to, benzene, toluene, hexanes, pentane, tetrahydrofuran,dialkylethers, 1,4-dioxane, chloroform, methylene chloride,1,2-dichloroethane, dimethylformamide, and mixtures thereof.

Method 6

Compounds of the formula (X) can be prepared by a two-step process thatincludes treatment of compounds of the formula (XI) and compounds of theformula (XII), where R1, R2, R3, R4, R5, A1, A2, and A3 are as definedabove, in a sealed tube to selectively displace the chlorine at position6. Condensation with a pyridine carboxaldehyde under Dean-Starkconditions catalyzed by para-toluenesulfonic acid produces the compoundof formula (X).

Method 7

Compounds of the formula (XIV) can be prepared by a two-step processthat includes treatment of compounds of the formula (XV) and compoundsof the formula (XVI), where R1, R2, R3, R4, A1, A2, and A3 are asdefined above, in a sealed tube to selectively displace the chlorine atposition 6. Condensation with a carboxaldehyde (R6CHO) under Dean-Starkconditions catalyzed by para-toluenesulfonic acid produces the compoundof formula XIV.

EXAMPLES

The examples are for illustration purposes and are not to be construedas limiting the invention disclosed in this document to only theembodiments disclosed in these examples.

Example I Preparation of6-[2-(2-Pyridyl)-1-pyrrolidinyl]-4-trifluoromethyl-2,3-dichloropyridine(Compound 1)

To a solution of 1.25 g (0.005 mol) of2,3,6-trichloro-4-trifluoromethypyridine in 7.5 mL of anhydrousp-dioxane was added 0.889 g (0.006 mol) of 2-(pyrrolidine-2-yl)pyridinefollowed by 0.97 g (0.0075 mol) of diisopropylethylamine. The mixturewas magnetically stirred and heated in a microwave chamber to 130° C.for 45 min. Upon cooling to room temperature, the red reaction mixturewas diluted with 50 mL of ethyl acetate, washed with a saturatedsolution of NaCl, and dried (MgSO₄). Solvent removal gave 1.81 g of a6:1 mixture of6-[2-(2-pyridyl)-1-pyrrolidinyl]-4-trifluoromethyl-2,5-dichloropyridine(Compound 2) and6-[2-(2-pyridyl)-1-pyrrolidinyl]-4-trifluoromethyl-2,3-dichloropyridine(Compound 1). Column chromatography on silica gel eluting with 20% ethylacetate/hexane gave 1.05 g of 98% pure Compound 2 and 0.41 g of 1:1mixture of Compound 2:Compound 1. This mixture was further separated asabove to give 0.18 g of Compound 2 and 0.15 g of Compound 1.

Compound 1: ¹H NMR (300 MHz, CDCl₃) δ 8.58 (dd, J=4.8, 1.0 Hz, 1H), 7.61(dt, J=2.0, 7.9 Hz, 1H), 7.17 (ddd, J=4.8, 2.0, 1.0 1H), 7.11 (d, J=7.9Hz, 1H), 6.40 (brs, 1H), 5.04 (brs, 1H), 3.83 (m, 1H), 3.65 (m, 1H),2.43 (m, 1H), 2.1 (m, 3H). Exact mass for C₁₅H₁₂C₂F₃N₃. Calcd, 316.0355.Found, 361.0358.

Compound 2: ¹H NMR (300 MHz, CDCl₃) δ 8.54 (dq, J=4.8, 1.0 Hz, 1H), 7.56(dt, J=2.0, 7.9 Hz, 1H), 7.24 (d, J=7.9 Hz, 1H), 7.16 (ddd, J=4.8, 2.0,1.0, 1H), 6.84 (brs, 1H), 5.50 (t, J=6.7 Hz, 1H), 4.22 (m, 1H), 3.81 (m,1H), 2.43 (m, 1H), 2.1 (m, 3H). Exact mass for C₁₅H₁₂Cl₂F₃N₃. Calcd,316.0355; Found, 361.0357.

Example II Preparation of2-(2-Pyridyl)piperidin-2-yl)-4-trifluoromethyl-5,6-dichloropyridine(Compound 6) and2-(2-Pyridyl)piperidin-2-yl)-4-trifluoromethyl-3,6-dichloropyridine(Compound 7)

To a solution of 1.25 g (0.005 mol) of2,3,6-trichloro-4-trifluoromethypyridine in 7.5 mL of anhydrousp-dioxane was added 0.973 g (0.006 mol) of 2-(piperidin-2-yl)pyridinefollowed by 0.97 g (0.0075 mol) of diisopropylethylamine. The mixturewas magnetically stirred and heated in a microwave chamber to 130° C.for 45 min. Upon cooling to room temperature, the red reaction mixturewas diluted with 50 mL of ethyl acetate, washed with a saturatedsolution of NaCl, and dried (MgSO₄). Solvent removal gave 2.0 g of a 3:2mixture of2-(2-pyridyl)piperidin-2-yl)-4-trifluoromethyl-5,6-dichloropyridine(Compound 6) and2-(2-pyridyl)piperidin-2-yl)-4-trifluoromethyl-3,6-dichloropyridine(Compound 7). A 0.20 g sample was purified on silica gel eluting with10% ethyl acetate/hexane to give 0.14 g of 1:1 mixture of Compound6:Compound 7, which could not be further purified.

Compound 6: ¹H NMR (300 MHz, CDCl₃) δ 8.58 (m, 1H), 7.60 (m, 1H), 7.0(m, 2H), 6.75 (brs, 1H), 5.04 (brs, 1H), 3.3 (m, 2H), 2.6 (m, 1H),1.5-2.2 (m, 5H).

Compound 7: ¹H NMR (300 MHz, CDCl₃) δ 8.54 (m, 1H), 7.56 m, 1H), 7.3 (m,1H), 7.1 (m, 2H), 7.05 (brs, 1H), 5.60 (m, 1H), 4.20 (m, 1H), 3.5 (m,1H), 2.60 (m, 1H), 1.5-2.1 (m, 4H).

Example III Preparation of2,6-Dichloro-4-trifluoromethyl-3-trimethylsilanylpyridine (Compound 8)

A dry 100 mL 3 neck rb flask was charged with diisopropylamine (2.15 mL,15.3 mmol) and 40 mL of anhydrous THF. Reaction mixture was cooled at−20° C. under N₂. A 2.5 M solution of n-BuLi in Hexane (5.90 mL, 14.8mmol) was added dropwise via a syringe. The resulting reaction mixturewas then cooled at −78° C. A solution of2,6-dichloro-4-trifluoromethylpyridine (3.0 g, 14 mmol) in 5 mL ofanhydrous THF was added slowly via an addition funnel to give a paleyellow solution. Reaction mixture stirred at −78° C. for 2 h. Afterwhich time, a solution of TMSCl (2.0 mL, 15.8 mmol) in 5 mL of THF wasadded dropwise via an addition funnel. The resulting reaction mixturewas allowed to slowly warm up to room temperature and stirred overnight. Reaction mixture was added to 150 mL of Et₂O, washed with diluteHCl, then washed with aq. NaHCO₃, dried over MgSO₄, filtered andconcentrated to give 3.80 g (95%) of2,6-dichloro-4-trifluoromethyl-3-trimethylsilanylpyridine (Compound 8)as a brown oil:

¹H NMR (300 MHz, CDCl₃) δ 0.5 (s, 9H), 7.55 (s, 1H).

Example IV Preparation of2-(2-Pyridyl)pyrrolidine-2-yl)-4-trifluoromethyl-5-trimethylsilanylpyridine-6-chloropyridine(Compound 10)

To a solution of 1.44 g (0.005 mol) of2,6-dichloro-4-trifluoromethyl-3-trimethylsilanylpyridine (Compound 8)in 7.5 mL of anhydrous p-dioxane was added 0.889 g (0.006 mol) of2-(pyrrolidine-2-yl)pyridine followed by 0.97 g (0.0075 mol) ofdiisopropylethylamine. The mixture was magnetically stirred and heatedin a microwave chamber to 150° C. for 1 hr. Upon cooling to roomtemperature, the red reaction mixture was diluted with 50 mL of ethylether, washed with a saturated solution of NaCl, and dried (MgSO₄).Solvent removal gave 2.05 g of an orange oil. Column chromatography onsilica gel eluting with 10% ethyl acetate/hexane gave 0.95 g (48% yield)of2-(2-pyridyl)pyrrolidine-2-yl)-4-trifluoromethyl-5-trimethylsilanylpyridine-6-chloropyridine(Compound 10).

¹H NMR (300 MHz, CDCl₃) δ 8.58 (dd, J=4.8, 1.0 Hz, 1H), 7.62 (dt, J=2.0,7.5 Hz, 1H), 7.15 (m, 2H), 6.45 (brs, 1H), 5.04 (brs, 1H), 3.8 (m, 1H),3.72 (m, 1H), 2.45 (m, 1H), 2.05-2.22 (m, 3H), 0.4 (s, 9H). Exact massfor C₁₅H₂₁ClF₃N₃Si. Calcd, 399.1140. Found, 399.1146.

Example V Preparation of2-(2-Pyridyl)pyrrolidino-2-yl)-4-trifluoromethyl-5-trimethylsilanylpyridinepyridine(Compound 11)

To a solution of 0.24 g (0.6 mmol)2-(2-pyridyl)pyrrolidino-2-yl)-4-trifluoromethyl-5-trimethylsilanylpyridine-6-chloropyridine(Compound 10) in 5 mL of methanol was added 0.252 g (4 mmol) of ammoniumformate followed by 0.1 g of 5% Pd on carbon. The mixture wasmagnetically stirred and heated in a microwave chamber to 100° C. for1.5 hr. Upon cooling to room temperature, the reaction mixture wasfiltered through a plug of Celite and solvent was removed. The residuewas dissolved in methylene chloride washed with a saturated solution ofNaCl and dried (MgSO₄). Solvent removal gave 0.185 g (84% yield) of a95% pure2-(2-pyridyl)pyrrolidine-2-yl)-4-trifluoromethyl-5-trimethylsilanylpyridinepyridine(Compound 11).

¹H NMR (300 MHz, CDCl₃) δ 8.58 (dd, J=4.8, 1.0 Hz, 1H), 8.37 (s, 1H),7.62 (dt, J=2.0, 7.5 Hz, 1H), 7.15 (m, 2H), 6.55 (brs, 1H), 5.20 (brs,1H), 3.91 (m, 1H), 3.70 (m, 1H), 2.45 (m, 1H), 2.22 (m, 1H), 2.10 (m2H), 0.4 (s, 9H). Exact mass for C₁₁H₂₂IF₃N₃Si. Calcd, 365.1535. Found,399.1532.

Example VI Synthesis of2-chloro-6-[4-isopropyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 12)

Step 1: Preparation of2-chloro-6-[[1-(hydroxymethyl)-2-methyl-propyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrileintermediate

Neat 3-cyano-2,6-dichloro-4-trifluoromethylpyridine (0.641 g, 6 mmol)(Compound 14) was added by pipette at a dropwise rate over 3 minutes to2-amino-3-methyl-butan-1-ol (1.5 g, 6 mmol) (Compound 15).Di-isopropylamine (0.9 g, 7 mmol) was added after 10 minutes and theresultant mixture was heated in a sealed tube at 70° C. for 30 minutesto selectively displace the chlorine at position 6 before quenching inice-cold water and extracted with dichloromethane. Organic extracts werewashed twice with water, dried over sodium sulfate and concentratedunder reduced pressure. The residue was washed with diethylether and theresultant solid was used in the next step without further purification.2-Chloro-6-[[1-(hydroxymethyl)-2-methyl-propyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 13) was isolated in 50% yield.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 6.66 (s, 1H), 5.63 (br, 1H), 4.09 (br,0.7H), 3.81 (t, J=4.5 Hz, 2.4H), 2.01 (octet, J=6.9 Hz, 1H), 1.70 (br t,J=4.9 Hz, 0.9H), 1.03 (d, J=6.7 Hz, 3H), 1.00 (d, J=6.8 Hz, 3H).

Step 2: Synthesis of2-chloro-6-[4-isopropyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile

Pyridine-2-carboxaldehyde (207 mg, 1.9 mmol) was added to a toluenesolution (15 mL) of2-chloro-6-[[1-(hydroxymethyl)-2-methyl-propyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrile(400 mg, 1.3 mmol) (Compound 13) followed by a catalytic amount ofpara-toluene sulfonic acid (50 mg). The reactants were refluxed for 6hours in a Dean-Stark apparatus, concentrated under reduced pressure,adsorbed onto silica and purified using a neutral alumina column,eluting with a mobile phase of 10% ethyl acetate in hexane.2-Chloro-6-[4-isopropyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 12) was isolated as a solid in 20% yield. mp 112-115° C.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 8.49 (br, 0.7H), 7.73 (dt, J¹=6.7 Hz,J²=1.8 Hz, 0.8H), 7.42 (br, 0.8H), 7.26 (br), 6.61 (br, 0.4H), 6.38 (br,0.9H), 4.52 (br, 1.5H), 4.21 (d, J=8.4 Hz, 1.3H), 2.42 (br, 0.8H), 1.06(d, J=6.6 Hz, 3H), 0.97 (d, J=6.6 Hz, 3-1); ES/MS 397.0 (M⁺).

Example VII Synthesis of2-chloro-6-[4-methyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 16)

Step 1: Synthesis of2-chloro-6-[[1-(hydroxymethyl)-2-methyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrile

Neat 3-cyano-2,6-dichloro-4-trifluoromethylpyridine (0.641 g, 6 mmol)was added by pipette at a dropwise rate over 3 minutes to2-aminopropanol (1.5 g, 6 mmol). Di-isopropylamine (0.9 g, 7 mmol) wasadded after 10 minutes and the resultant mixture was heated in a sealedtube at 70° C. for 30 minutes to selectively displace the chlorine atposition 6 before quenching in ice-cold water and extracted withdichloromethane. Organic extracts were washed twice with water, driedover sodium sulfate and concentrated under reduced pressure. The residuewas washed with diethylether and the resultant solid was used in thenext step without further purification.2-Chloro-6-[[1-(hydroxymethyl)-2-methyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrilewas isolated in 52% yield.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 6.63 (s, 1H), 4.27 (br, 0.8H), 3.84-3.79(m, 1.2H), 3.70-3.65 (m, 1.3H), 1.80 (br t, 0.8H), 1.58 (s, 1.3H), 1.30(d, J=6.7 Hz, 3H).

Step 2: Synthesis of2-chloro-6-[4-methyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile

Pyridine-2-carboxaldehyde (207 mg, 1.9 mmol) was added to a toluenesolution (15 mL) of2-chloro-6-[[1-(hydroxymethyl)-2-methyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrile(400 mg, 1.3 mmol) followed by a catalytic amount of para-toluenesulfonic acid (50 mg). The reactants were refluxed for 6 hours in aDean-Stark apparatus, concentrated under reduced pressure, adsorbed ontosilica and purified using a neutral alumina column, eluting with amobile phase of 10% ethyl acetate in hexane.2-Chloro-6-[4-methyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 16) was isolated as a solid in 55% yield. mp 90-93° C.

¹HNMR (CDCl₃, 400 MHz) S/ppm 8.63 (d, J=4.8 Hz, 0.2H), 8.52 (br, 0.6H),7.78-7.73 (m, 1H), 7.54 (d, J=7.9 Hz, 0.2H), 7.43 (br, 0.8H), 7.34-7.26(m), 6.85 (br, 0.2H), 6.67 (m, 0.5H), 6.42-6.17 (br, 1.4H), 4.71-4.43(br, 2H), 4.29 (t, 0.3H), 4.11-4.10 (m, 0.2H), 3.98 (d, J=8.2 Hz, 1H),1.49 (d, J=6.3 Hz, 3H); ES/MS 369.0 (M⁺).

Example VIII Synthesis of2-chloro-6-[5-ethyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 17)

Step 1: Synthesis of2-chloro-6-(2-hydroxybutylamino)-4-(trifluoromethyl)pyridine-3-carbonitrile

Neat 3-cyano-2,6-dichloro-4-trifluoromethylpyridine (0.641 g, 6 mmol)was added by pipette at a dropwise rate over 3 minutes to 2-aminobutanol(1.5 g, 6 mmol). Di-isopropylamine (0.9 g, 7 mmol) was added after 10minutes and the resultant mixture was heated in a sealed tube at 70° C.for 30 minutes to selectively displace the chlorine at position 6 beforequenching in ice-cold water and extracted with dichloromethane. Organicextracts were washed twice with water, dried over sodium sulfate andconcentrated under reduced pressure. The residue was washed withdiethylether and the resultant solid was used in the next step withoutfurther purification.2-Chloro-6-(2-hydroxybutylamino)-4-(trifluoromethyl)pyridine-3-carbonitrilewas isolated in 55% yield.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 6.64 (s, 1H), 5.96 (br, 1H), 3.78 (br, 1H),3.32 (br, 1H), 1.94 (br d, J=4.1 Hz, 1H), 1.65-1.50 (m, 4H), 1.02 (t,J=7.5 Hz, 3H).

Step 2: Synthesis of2-chloro-6-[5-ethyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile

Pyridine-2-carboxaldehyde (207 mg, 1.9 mmol) was added to a toluenesolution (15 mL) of2-chloro-6-(2-hydroxybutylamino)-4-(trifluoromethyl)pyridine-3-carbonitrile(400 mg, 1.3 mmol) followed by a catalytic amount of para-toluenesulfonic acid (50 mg). The reactants were refluxed for 6 hours in aDean-Stark apparatus, concentrated under reduced pressure, adsorbed ontosilica and purified using a neutral alumina column, eluting with amobile phase of 10% ethyl acetate in hexane.2-Chloro-6-[5-ethyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 17) was isolated as a solid in 37% yield. mp 115-118° C.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 8.59 (d, J=4.5 Hz, 0.7H), 7.76 (t, J=7.5Hz, 0.8; H), 7.46 (dd, J¹=7.8 Hz, J²=1.0 Hz, 0.8H), 7.31 (br, 0.7H),6.84 (br, 0.6H), 6.66 (br, 0.2H), 6.12 (br, 0.7H), 4.75 (br, 0.1H), 4.44(br, 0.6H), 4.24 (br, 0.9H), 4.03 (t, J=9.6 Hz, 0.3H), 3.53 (br, 1H),1.97-1.80 (m, 2.1H), 1.10-1.02 (m, 3H); ES/MS 383.0 (M⁺).

Example IX2-chloro-6-[4-phenyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 18)

Step 1: Synthesis of2-chloro-6-[[1-(hydroxymethyl)-2-phenyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrile

Neat 3-cyano-2,6-dichloro-4-trifluoromethylpyridine (0.641 g, 6 mmol)was added by pipette at a dropwise rate over 3 minutes to2-amino-2-phenylethanol (1.5 g, 6 mmol). Di-isopropylamine (0.9 g, 7mmol) was added after 10 minutes and the resultant mixture was heated ina sealed tube at 70° C. for 30 minutes to selectively displace thechlorine at position 6 before quenching in ice-cold water and extractedwith dichloromethane. Organic extracts were washed twice with water,dried over sodium sulfate and concentrated under reduced pressure. Theresidue was washed with diethylether and the resultant solid was used inthe next step without further purification.2-Chloro-6-[[1-(hydroxymethyl)-2-phenyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrilewas isolated in 60% yield.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 7.42-7.33 (m, 5H), 6.51 (br, 2H), 4.06-4.03(m, 1.4H), 3.96 (br, 1.1H), 1.89 (br, 0.96H), 1.60 (m, 1.1H).

Step 2: Synthesis of2-chloro-6-[4-phenyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile

Pyridine-2-carboxaldehyde (207 mg, 1.9 mmol) was added to a toluenesolution (15 mL) of2-chloro-6-[[1-(hydroxymethyl)-2-phenyl]amino]-4-(trifluoromethyl)pyridine-3-carbonitrile(400 mg, 1.3 mmol) followed by a catalytic amount of para-toluenesulfonic acid (50 mg). The reactants were refluxed for 6 hours in aDean-Stark apparatus, concentrated under reduced pressure, adsorbed ontosilica and purified using a neutral alumina column, eluting with amobile phase of 10% ethyl acetate in hexane.2-Chloro-6-[4-phenyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 18) was isolated as a solid in 19% yield. mp 198-200° C.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 8.53 (br, 0.8H), 7.79 (dt, J¹=7.6 Hz,J²=1.4 Hz, 1H), 7.57 (br, 1.1H), 7.42-7.37 (m, 7.2H), 7.29 (br), 6.78(br, 0.9H), 6.43 (br, 1.2H), 5.60 (br, 0.2H), 5.23 (br, 1H), 5.00 (br,1.1H), 4.17-4.13 (m, 1.4H); ES/MS 431.0 (M⁺).

Example X2-Chloro-6-[5-ethyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 19)

Step 1: Synthesis of2-chloro-6-(2-hydroxybutylamino)-4-(trifluoromethyl)pyridine-3-carbonitrile

Neat 3-cyano-2,6-dichloro-4-trifluoromethylpyridine (0.641 g, 6 mmol)was added by pipette at a dropwise rate over 3 minutes to1-aminopropane-2-ol (1.5 g, 6 mmol). Di-isopropylamine (0.9 g, 7 mmol)was added after 10 minutes and the resultant mixture was heated in asealed tube at 70° C. for 30 minutes to selectively displace thechlorine at position 6 before quenching in ice-cold water and extractedwith dichloromethane. Organic extracts were washed twice with water,dried over sodium sulfate and concentrated under reduced pressure. Theresidue was washed with diethylether and the resultant solid was used inthe next step without further purification.

2-chloro-6-(2-hydroxybutylamino)-4-(trifluoromethyl)pyridine-3-carbonitrilewas isolated in 55% yield. ¹HNMR (CDCl₃, 400 MHz) δ/ppm 6.64 (s, 1H),5.63 (br, 1H), 4.21 (br, 0.7H), 3.83-3.73 (m, 2.5H), 2.18 (d, J=0.8 Z,2H), 1.76-1.61 (m, 3.2H), 1.54-1.51 (m, 0.6H), 1.44 (d, J=6.7 Hz, 0.3H),1.00 (t, J=7.4 Hz, 3H).

Step 2: Synthesis of2-chloro-6-[5-ethyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile

Pyridine-2-carboxaldehyde (207 mg, 1.9 mmol) was added to a toluenesolution (15 mL) of2-chloro-6-(2-hydroxybutylamino)-4-(trifluoromethyl)pyridine-3-carbonitrile(400 mg, 1.3 mmol) followed by a catalytic amount of para-toluenesulfonic acid (50 mg). The reactants were refluxed for 6 hours in aDean-Stark apparatus, concentrated under reduced pressure, adsorbed ontosilica and purified using a neutral alumina column, eluting with amobile phase of 10% ethyl acetate in hexane.2-Chloro-6-[5-ethyl-2-(2-pyridyl)oxazolidin-3-yl]-4-(trifluoromethyl)pyridine-3-carbonitrile(Compound 19) was isolated as a solid in 46% yield. mp 99-102° C.

¹HNMR (CDCl₃, 400 MHz) δ/ppm 8.62-8.63 (m, 0.4H), 8.51 (br, 0.2H),7.79-7.74 (m, 0.8H), 7.54 (d, J=7.9 Hz, 0.5H), 7.42 (br, 0.3H),7.34-7.31 (m, 0.5H), 6.92 (br, 0.5H), 6.64 (br, 0.2H), 6.40 (br, 0.4H),6.12 (br, 0.5H), 4.66 (br, 0.4H), 4.38 (br, 0.6H), 4.21-4.20 (m, 1.4H),4.11 (d, J=8.6 Hz, 0.5H); 2.09-1.98 (m 0.8H), 1.87-1.78 (m, 1.3H),1.05-1.00 (m, 3H); ES/MS 383.0 (M⁺).

Example XI Insecticidal Testing

Insecticidal Test for Green Peach Aphid (Myzus persicae) in Foliar SprayAssay

Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) trueleaves, were used as test substrate. The seedlings were infested with20-50 green peach aphids (wingless adult and nymph) 1-2 days prior tochemical application. Four seedlings were used for each treatment.Selected compounds (2 mg), many of which are described above, weredissolved in 2 ml of acetone:methanol (1:1) solvent, forming stocksolutions of 1000 ppm. The stock solutions were diluted 5× with 0.025%Tween 20 in H₂O to obtain a solution at 200 ppm. A hand-held Devilbissaspirator sprayer was used for spraying a solution to both sides ofcabbage leaves until runoff. Reference plants (solvent check) weresprayed with the diluent only. Treated plants were held in a holdingroom for three days at approximately 23° C. and 40% relative humidityprior to grading. Evaluation was conducted by counting the number oflive aphids per plant under a microscope.

Insecticidal activity was measured by using Abbott's correction formula:

Corrected % Control=100*(X−Y)/X

-   -   where        -   X=No. of live aphids on solvent check plants        -   Y=No. of live aphids on treated plants

The results of this test are set forth in the column labelled “GreenPeach Aphid” in Table 1 below, in which letter designations representranges of percent control as follows:

-   -   A=80-100% control    -   B=60-79% control    -   C=40-59% control    -   D=20-39% control    -   E=0-19% control    -   Insecticidal test for beet armyworm (Spodoptera exigua).

To prepare test solution, the test compound was formulated at 2000 ppmsolution in 2 mL of 9 acetone: 1 tap water. 50 μL of the test solution(50 g/cm² dose for each well) was pipetted upon the surface of 1 mL oflepidopteran diet (Southland Multi-Species Lepidopteran Diet) containedin each of eight wells per insect species (one well=1 replication). Asecond-instar beet armyworm was placed upon the treated diet in eachwell (one insect per well) once the solvent had air-dried. Trayscontaining the treated diet and larvae were covered and then held in agrowth chamber at 25° C., 50-55% RH, and 16 hr light:8 hr dark for 5days. Observation were conducted 2 and 5 days after treatment andinfestation to score the number of dead insects per 8-well treatment.

The results of this test are set forth in the column labelled “BeetArmyworm” in Table 1 below, in which letter designations representranges of percent control as set forth above.

TABLE 1 Beet Green Compound Army- Peach No. STRUCTURE worm Aphid  1

B A  2

B C

D D  6

A D 10

E E

E D 11

A A

D E

B E 16

E E 17

E E 12

E D 18

E E 19

C C

Acid & Salt Derivatives, and Solvates

The compounds of Formula I can be in the form of pesticidally acceptableacid addition salts.

By way of non-limiting example, an amine function can form salts withhydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic,citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartaric,lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic,methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, andhydroxyethanesulfonic, acids.

Additionally, by way of non-limiting example, an acid function can formsalts including those derived from alkali or alkaline earth metals andthose derived from ammonia and amines. Examples of preferred cationsinclude sodium, potassium, magnesium, and aminium cations.

The salts are prepared by contacting the free base form with asufficient amount of the desired acid to produce a salt. The free baseforms may be regenerated by treating the salt with a suitable diluteaqueous base solution such as dilute aqueous NaOH, potassium carbonate,ammonia, and sodium bicarbonate.

As an example, in many cases, a pesticide is modified to a more watersoluble form e.g. 2,4-dichlorophenoxy acetic acid dimethyl amine salt isa more water soluble form of 2,4-dichlorophenoxy acetic acid a wellknown herbicide.

The compounds disclosed in this application can also form stablecomplexes with solvent molecules that remain intact after thenon-complexed solvent molecules are removed from the compounds. Thesecomplexes are often referred to as “solvates”.

Stereoisomers

Certain compounds disclosed in this application can exist as one or morestereoisomers. The various stereoisomers include geometric isomers,diastereomers, and enantiomers. Thus, the compounds disclosed in thisapplication include racemic mixtures, individual stereoisomers, andoptically active mixtures.

It will be appreciated by those skilled in the art that one stereoisomermay be more active than the others. Individual stereoisomers andoptically active mixtures may be obtained by selective syntheticprocedures, by conventional synthetic procedures using resolved startingmaterials, or by conventional resolution procedures.

Bests

In another embodiment, the invention disclosed in this document can beused to control pests.

In another embodiment, the invention disclosed in this document can beused to control pests of the Phylum Nematoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Phylum Arthropoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Chelicerata.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Arachnida.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Myriapoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Symphyla.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Hexapoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Insecta.

In another embodiment, the invention disclosed in this document can beused to control Coleoptera (beetles). A non-exhaustive list of thesepests includes, but is not limited to, Acanthoscelides spp. (weevils),Acanthoscelides obtectus (common bean weevil), Agrilus planipennis(emerald ash borer), Agriotes spp. (wireworms), Anoplophora glabripennis(Asian longhorned beetle), Anthonomus spp. (weevils), Anthonomus grandis(boll weevil), Aphidius spp., Apion spp. (weevils), Apogonia spp.(grubs), Ataenius sprelulus (Black Turgrass Ataenius), Atomaria linearis(pygmy mangold beetle), Aulacophore spp., Bothynoderes punctiventris(beet root weevil), Bruchus spp. (weevils), Bruchus pisorum (peaweevil), Cacoesia spp., Callosobruchus maculatus (southern cow peaweevil), Carpophilus hemipteras (dried fruit beetle), Cassida vittata,Cerosterna spp., Cerotoma spp. (chrysomeids), Cerotoma trifurcata (beanleaf beetle), Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis(cabbage seedpod weevil), Ceutorhynchus napi (cabbage curculio),Chaetocnema spp. (chrysomelids), Colaspis spp. (soil beetles), Conoderusscalaris, Conoderus stigmosus, Conotrachelus nenuphar (plum curculio),Cotinus nitidis (Green June beetle), Crioceris asparagi (asparagusbeetle), Cryptolestes ferrugineus (rusty grain beetle), Cryptolestespusillus (flat grain beetle), Cryptolestes turcicus (Turkish grainbeetle), Ctenicera spp. (wireworms), Curculio spp. (weevils),Cyclocephala spp. (grubs), Cylindrocpturus adspersus (sunflower stemweevil), Deporaus marginatus (mango leaf-cutting weevil), Dermesteslardarius (larder beetle), Dermestes maculates (hide beetle), Diabroticaspp. (chrysolemids), Epilachna varivestis (Mexican bean beetle),Faustinus cubae, Hylobius pales (pales weevil), Hvpera spp. (weevils),Hypera postica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys fuscus, Liogenys suturalis,Lissorhopirus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothedgrain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabhana, Phyllotreta spp.(chrysomelids), Phynchites spp. Popillia japonica (Japanese beetle),Prostephanus truncates (larger grain borer), Rhizopertha dominica(lesser grain borer), Rhizotrogus spp. (Eurpoean chafer), Rhynchophorusspp. (weevils), Scolytus spp. (wood beetles), Shenophorus spp.(Billbug), Sitona lineatus (pea leaf weevil), Sitophilus spp. (grainweevils), Sitophilus granaries (granary weevil), Sitophilus oryzae (riceweevil), Stegobium paniceum (drugstore beetle), Tribolium spp. (flourbeetles), Tribolium castaneum (red flour beetle), Tribolium confusum(confused flour beetle), Trogoderma variabile (warehouse beetle), andZabrus tenebioides.

In another embodiment, the invention disclosed in this document can beused to control Dermaptera (earwigs).

In another embodiment, the invention disclosed in this document can beused to control Dictyoptera (cockroaches). A non-exhaustive list ofthese pests includes, but is not limited to, Blattella germanica (Germancockroach), Blatta orientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaaustraloasiae (Australian cockroach), Periplanela brunnea (browncockroach), Periplaneta idliginosa (smokybrown cockroach), Pvncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In another embodiment, the invention disclosed in this document can beused to control Diptera (true flies). A non-exhaustive list of thesepests includes, but is not limited to, Aedes spp (mosquitoes), Agromyzafrontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner flies),Anastrepha spp. (fruit flies), Anastrepha suspensa (Caribbean fruitfly), Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies),Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (oriental fruitfly), Ceratitis spp. (fruit flies), Ceratitis capitata (Mcditcrrancafruit fly), Chrysops spp. (deer flies), Cochliomyia spp. (screwworms),Contarinia spp. (Gall midges), Culex spp. (mosquitoes), Dasineura spp.(gall midges), Dasineura brassicae (cabbage gall midge), Delia spp.,Delia platura (seedcorn maggot), Drosophila spp. (vinegar flies), Fanniaspp. (filth flies), Fannia canicularis (little house fly), Fanniascalaris (latrine fly), Gasterophilus intestinalis (horse bot fly),Gracillia perseae, Haematobia irritans (horn fly), Hylemyia spp. (rootmaggots), Hypoderma lineatum (common cattle grub), Liriomyza spp.(leafminer flies), Liriomyza brassica (serpentine leafminer), Melophagusovinus (sheep ked), Musca spp. (muscid flies), Musca autumnalis (facefly), Musca domestica (house fly), Oestrus ovis (sheep bot fly),Oscinella frit (frit fly), Pegomyia betae (beet leafminer), Phorbiaspp., Psila rosae (carrot rust fly), Rhagoletis cerasi (cherry fruitfly), Rhagoletis pomonella (apple maggot), Sitodiplosis mosellana(orange wheat blossom midge), Stomoxys calcitrans (stable fly), Tabanusspp. (horse flies), and Tipula spp. (crane flies).

In another embodiment, the invention disclosed in this document can beused to control Hemiptera (true bugs). A non-exhaustive list of thesepests includes, but is not limited to, Acrosternum hilare (green stinkbug), Blissus leucopterus (chinch bug), Calocoris norvegicus (potatomirid), Cimex hemipterus (tropical bed bug), Cimex lectularius (bedbug), Dagbertus fasciatus, Dichelops furcatus, Dysdercus suturellus(cotton stainer), Edessa meditabunda, Eurygaster maura (cereal bug).Euschistus heros, Euschistus servus (brown stink bug), Helopeltisantonii, Helopeltis theivora (tea blight plantbug), Lagynotomus spp.(stink bugs), Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp.(plant bugs), Lygus hesperus (western tarnished plant bug),Maconellicoccus hirsutus, Neurocolpus longirostris, Nezara viridula(southern green stink bug), Phytocoris spp. (plant bugs), Phytocoriscalifornicus, Phytocoris relativus, Piezodorus guildingi, Poecilocapsuslineatus (fourlined plant bug), Psallus vaccinicola, Pseudacystaperseae, Scaptocoris castanea, and Triatoma spp. (bloodsucking conenosebugs/kissing bugs).

In another embodiment, the invention disclosed in this document can beused to control Homoptera (aphids, scales, whiteflies, leafhoppers). Anon-exhaustive list of these pests includes, but is not limited to,Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodesproletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixusfloccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutellabigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii(California red scale), Aphis spp. (aphids), Aphis gossypii (cottonaphid), Aphis pomi (apple aphid), Aulacorthun solani (foxglove aphid),Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia tabaci(sweetpotato whitefly), Brachycolus noxius (Russian aphid),Brachycorynella asparagi (asparagus aphid), Brevennia rehi, Brevicorynebrassicae (cabbage aphid), Ceroplastes spp. (scales), Ceroplastes rubens(red wax scale), Chionaspis spp. (scales). Chrysomphalus spp. (scales),Coccus spp. (scales), Dysaphis plantaginea (rosy apple aphid), Empoascaspp. (leafhoppers), Eriosoma lanigerum (woolly apple aphid), Iceryapurchasi (cottony cushion scale), Idioscopus nitidulus (mangoleafhopper), Laodelphax striatellus (smaller brown planthopper),Lepidosaphes spp., Macrosiphum spp., Macrosiphum euphorbiae (potatoaphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosae(rose aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarvafrimbiolata, Metopolophium dirhodum (rose grain aphid), Mictislongicornis, Myzus persicae (green peach aphid), Nephotettix spp.(leafhoppers), Nephotettix cinctipes (green leafhopper), Nilaparvatalugens (brown planthopper), Parlatoria pergandii (chaff scale),Parlatoria ziziphi (ebony scale), Peregrinus maidis (corn delphacid),Philaenus spp. (spittlebugs), Phylloxera vitifoliae (grape phylloxera),Physokermes piceae (spruce bud scale), Planococcus spp. (mealybugs),Pseudococcus spp. (mealybugs), Pseudococcus brevipes (pine applemealybug), Quadraspidiotus perniciosus (San Jose scale), Rhapalosiphumspp. (aphids), Rhapalosiphum maida (corn leaf aphid), Rhapalosiphum padi(oat bird-cherry aphid), Saissetia spp. (scales), Saissetia oleae (blackscale), Schizaphis graminum (greenbug), Sitobion avenae (English grainaphid), Sogatella furcifera (white-backed planthopper), Therioaphis spp.(aphids), Toumeyella spp. (scales), Toxoptera spp. (aphids),Trialeurodes spp. (whiteflies), Trialeurodes vaporariorum (greenhousewhitefly), Trialeurodes abutiloneus (bandedwing whitefly), Unaspis spp.(scales), Unaspis yanonensis (arrowhead scale), and Zulia entreriana.

In another embodiment, the invention disclosed in this document can beused to control Hymenoptera (ants, wasps, and bees). A non-exhaustivelist of these pests includes, but is not limited to, Acromyrrmex spp.,Athalia rosae, Atta spp. (leafcutting ants), Camponotus spp. (carpenterants), Diprion spp. (sawflies), Formica spp. (ants), Iridomyrmex humilis(Argentine ant), Monomorium ssp., Monomorium minumum (little black ant),Monomorium pharaonis (Pharaoh ant), Neodiprion spp. (sawflies),Pogonomyrmex spp. (harvester ants), Polistes spp. (paper wasps),Solenopsis spp. (fire ants), Tapoinoma sessile (odorous house ant),Tetranomorium spp. (pavement ants), Vespula spp. (yellow jackets), andXylocopa spp. (carpenter bees).

In another embodiment, the invention disclosed in this document can beused to control Isoptera (termites). A non-exhaustive list of thesepests includes, but is not limited to, Coptotermes spp., Coptotermescurvignathus, Coptotermes frenchii, Coptotermes formosanus (Formosansubterranean termite). Cornitermes spp. (nasute termites), Cryptotermesspp. (drywood termites), Heterotermes spp. (desert subterraneantermites), Heterotermes aureus, Kalotermes spp. (drywood termites),Incistitermes spp. (drywood termites). Macrotermes spp. (fungus growingtermites), Marginitermes spp. (drywood termites), Microcerotermes spp.(harvester termites), Microtermes obesi, Procornitermes spp.,Reticulitermes spp. (subterranean termites), Reticulitermes banyulensis,Reticulitermes grassei, Reticulitermes flavipes (eastern subterraneantermite), Reticulitermes hageni, Reticulitermes hesperus (westernsubterranean termite), Reticulitermes santonensis, Reticulitermessperatus, Reticulitermes tibialis, Reticulitermes virginicus,Schedorhinotermes spp., and Zootermopsis spp. (rotten-wood termites).

In another embodiment, the invention disclosed in this document can beused to control Lepidoptera (moths and butterflies). A non-exhaustivelist of these pests includes, but is not limited to, Achoea janata,Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotisipsilon (black cutworm), Alabama argillacea (cotton leafworm), Amorbiacuneana, Amyelosis transitella (navel orangeworm), Anacamptodesdefectaria, Anarsia lineatella (peach twig borer), Anomis sabulifera(jute looper), Anticarsia gemmatalis (velvetbean caterpillar), Archipsargyrospila (fruit tree leafroller), Archips rosana (rose leaf roller),Argyrotaenia spp. (tortricid moths), Argyrotaenia citrana (orangetortrix), Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaffolder), Bucculatrix thurberiella (cotton leaf perforator), Calopliliaspp. (leaf miners), Capua reticulana, Carposina niponensis (peach fruitmoth), Chilo spp., Chlumetia transversa (mango shoot borer),Choristoneura rosaceana (oblique banded leaf roller), Chrysodeixis spp.,Cnaphalocerus medinalis (grass leafroller), Colias spp., Conpomorphacramerella, Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydia funebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),Diatraea saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Earias insulata(Egyptian bollworm), Earias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma saucia (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonorycler spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarpa, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiphusia nu, Scirpophagaincertulas. Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens. Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers). Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth). Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera cofeae (red branch borer), andZeuzera pyrina (leopard moth).

In another embodiment, the invention disclosed in this document can beused to control Mallophaga (chewing lice). A non-exhaustive list ofthese pests includes, but is not limited to, Bovicola ovis (sheep bitinglouse), Menacanthus stramineus (chicken body louse), and Menopongallinea (common hen house).

In another embodiment, the invention disclosed in this document can beused to control Orthoptera (grasshoppers, locusts, and crickets). Anon-exhaustive list of these pests includes, but is not limited to,Anabrus simplex (Mormon cricket), Gryllotalpidae (mole crickets),Locusta migratoria, Melanoplus spp. (grasshoppers), Microcentrumretinerve (angular winged katydid), Pterophylla spp. (kaydids),chistocerca gregaria, Scudderia furcata (fork tailed bush katydid), andValanga nigricorni.

In another embodiment, the invention disclosed in this document can beused to control Phthiraptera (sucking lice). A non-exhaustive list ofthese pests includes, but is not limited to, Haematopinus spp. (cattleand hog lice), Linognathus ovillus (sheep louse), Pediculus humanuscapitis (human body louse), Pediculus humanus humanus (human body lice),and Pthirus pubis (crab louse),

In another embodiment, the invention disclosed in this document can beused to control Siphonaptera (fleas). A non-exhaustive list of thesepests includes, but is not limited to, Ctenocephalides canis (dog flea),Ctenocephalides felis (cat flea), and Pulex irritans (human flea).

In another embodiment, the invention disclosed in this document can beused to control Thysanoptera (thrips). A non-exhaustive list of thesepests includes, but is not limited to, Frankliniella fusca (tobaccothrips), Frankliniella occidentalis (western flower thrips),Frankliniella shultzei Frankliniella williamsi (corn thrips),Heliothrips haemorrhaidalis (greenhouse thrips), Riphiphorothripscruentatus, Scirtothrips spp., Scirtothrips citri (citrus thrips),Scirtothrips dorsalis (yellow tea thrips). Taeniothripsrhopalantennalis, and Thrips spp.

In another embodiment, the invention disclosed in this document can beused to control Thysanura (bristletails). A non-exhaustive list of thesepests includes, but is not limited to, Lepisma spp. (silverfish) andThermobia spp. (firebrats).

In another embodiment, the invention disclosed in this document can beused to control Acarina (mites and ticks). A non-exhaustive list ofthese pests includes, but is not limited to, Acarapsis woodi (trachealmite of honeybees), Acarus spp. (food mites), Acarus siro (grain mite),Aceria mangiferae (mango bud mite), Aculops spp. Aculops lycopersici(tomato russet mite), Aculops pelekasi, Aculus pelekassi, Aculusschlechtendali (apple rust mite), Amblyomma americanum (lone star tick),Boophilus spp. (ticks), Brevipalpus obovatus (privet mite), Brevipalpusphoenicis (red and black flat mite), Demodex spp. (mange mites),Dermacentor spp. (hard ticks), Dermacentor variabilis (american dogtick), Dermatophagoides pteronyssinus (house dust mite), Eotetranycusspp., Eotetranychus carpini (yellow spider mite), Epitimerus spp.,Eriophyes spp., Ixodes spp. (ticks), Metatetranycus spp., Notoedrescati, Oligonychus spp., Oligonychus coffee, Oligonychus ilicus (southernred mite), Panonychus spp., Panonychus citri (citrus red mite),Panonychus ulmi (European red mite), Phyllocoptruta oleivora (citrusrust mite), Polyphagotarsonemun latus (broad mite), Rhipicephalussanguineus (brown dog tick), Rhizoglyphus spp. (bulb mites), Sarcoptesscabiei (itch mite), Tegolophus perseaflorae, Tetranychus spp.,Tetranychus urticae (twospotted spider mite), and Varroa destructor(honey bee mite).

In another embodiment, the invention disclosed in this document can beused to control Nematoda (nematodes). A non-exhaustive list of thesepests includes, but is not limited to, Aphelenchoides spp. (bud and leaf& pine wood nematodes), Belonolaimus spp. (sting nematodes),Criconemella spp. (ring nematodes), Dirofilaria immitis (dog heartworm),Ditylenchus spp. (stem and bulb nematodes), Heterodera spp. (cystnematodes), Heterodera zeae (corn cyst nematode), Hirschmanniella spp.(root nematodes), Hoplolaimus spp. (lance nematodes), Meloidogyne spp.(root knot nematodes), Meloidogyne incognita (root knot nematode),Onchocerca volvulus (hook-tail worm), Pratylenchus spp (lesionnematodes), Radopholus spp. (burrowing nematodes), and Rotylenchusreniformis (kidney-shaped nematode).

In another embodiment, the invention disclosed in this document can beused to control Symphyla (symphylans). A non-exhaustive list of thesepests includes, but is not limited to, Scutigerella immaculata.

For more detailed information consult “HANDBOOK OF PEST CONTROL—THEBEHAVIOR, LIFE HISTORY, AND CONTROL OF HOUSEHOLD PESTS” by ArnoldMallis, 9th Edition, copyright 2004 by GIE Media Inc.

Mixtures

The compounds of Formula I can also be used with various insecticides,both for reasons of economy and synergy. Such insecticides include, butare not limited to, antibiotic insecticides, macrocyclic lactoneinsecticides (for example, avernmectin insecticides, milbemycininsecticides, and spinosyn insecticides), arsenicual insecticides,botanical insecticides, carbamate insecticides (for example,benzofuranyl methylcarbamate insecticides, dimethylcarbamateinsecticides, oxime carbamate insecticides, and phenyl methylcarbamateinsecticides), diamide insecticides, desiccant insecticides,dinitrophenol insecticides, fluorine insecticides, formamidineinsecticides, fumigant insecticides, inorganic insecticides, insectgrowth regulators (for example, chitin synthesis inhibitors, juvenilehormone mimics, juvenile hormones, moulting hormone agonists, moultinghormones, moulting inhibitors, precocenes, and other unclassified insectgrowth regulators), nereistoxin analogue insecticides, nicotinoidinsecticides (for example, nitroguanidine insecticides, nitromethyleneinsecticides, and pyridylmethylamine insecticides), organochlorineinsecticides, organophosphorus insecticides, oxadiazine insecticides,oxadiazolone insecticides, phthalimide insecticides, pyrazoleinsecticides, pyrethroid insecticides, pyrimidinamine insecticides,pyrrole insecticides, tetramic acid insecticides, tetronic acidinsecticides, thiazole insecticides, thiazolidine insecticides, thioureainsecticides, urea insecticides, as well as, other unclassifiedinsecticides.

Some of the particular insecticides that can be employed beneficially incombination with the compounds of Formula I include, but are not limitedto, the following:—1,2-dichloropropane, abamectin, acephate,acetamiprid, acethion, acctoprole, acrinathrin, acrylonitrile,alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin,allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan,amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine,athidathion, azadirachtin, azamethiphos, azinphos-ethyl,azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin,bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin,bifenthrin, bioallethrin, bioethanomethrin, biopermethrin,bistrifluoron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT,bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb,butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calciumarsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl,carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion,carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole,chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeformhydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim,chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos,chromafenozide, cinerin I, cinerin II, cinerins, cismethrin,cloethocarb, closantel, clothianidin, copper acetoarsenite, copperarsenate, copper naphthenate, copper oleate, coumaphos, coumithoate,crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos,cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin,cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT,decarbofuran, deltamethrin, demephion, demephion-O, demephion-S,demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos,diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos,dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor,dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos,dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran,diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton,dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium,DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate,EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb,ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate,ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide,etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid,flubendiamide (additionally resolved isomers thereof), flucofuron,flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox,fluvalinate, fonofos, formetanate, formetanate hydrochloride,formothion, formparanate, formparanate hydrochloride, fosmethilan,fospirate, fosthietan, fufenozide, furathiocarb, furethrin,gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon,hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin,indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos,isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane,isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos,juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan,kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben,mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan,mercurous chloride, mesulfenfos, metaflumizone, methacrifos,methamidophos, methidathion, methiocarb, methocrotophos, methomyl,methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide,methyl isothiocyanate, methylchloroform, methylene chloride,metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate,milbemectin, milbemycin oxime, mipafox, mirex, molosultap,monocrotophos, monomehypo, monosultap, morphothion, moxidectin,naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram,nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene,parathion, parathion-methyl, penfluoron, pentachlorophenol, permethrin,phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan,phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl,pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassiumarsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I,precocene II, precocene III, primidophos, profenofos, profluralin,profluthrin, promacyl, promecarb, propaphos, propetamphos, propoxur,prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I,pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion,pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen,quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,resmethrin, rotenone, ryania, sabadilla, schradan, selamectin,silafluofen, silica gel, sodium arsenite, sodium fluoride, sodiumhexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad,spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid,sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate,tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, tetramethylfluthrin,theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime,thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon,thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin,tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene,triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat,trifenofos, tritlumuron, trimethacarb, triprene, vamidothion,vaniliprole, XMC, xylylcarb, zeta-cypermethrin, and zolaprofos.

Additionally, any combination of the above insecticides can be used.

The compounds of Formula I can also be used with herbicides andfungicides, or both for reasons of economy and synergy.

The compounds of Formula I can also be used, for reasons of economy andsynergy, with acaricides, algicides, antifeedants, avicides,bactericides, bird repellents, chemosterilants, fungicides, herbicidesafeners, herbicides, insect attractants, insect repellents, mammalrepellents, mating disrupters, molluscicides, plant activators, plantgrowth regulators, rodenticides, synergists, defoliants, desiccants,disinfectants, semiochemicals, and virucides (these categories notnecessarily mutually exclusive).

For more information consult “COMPENDIUM OF PESTICIDE COMMON NAMES”located at http://www.alanwood.net/pesticides/index.html. Also consult“THE PESTICIDE MANUAL” 14th Edition, edited by C D S Tomlin, copyright2006 by British Crop Production Council.

Synergistic Mixtures

The compounds of Formula I can be used with other compounds such as theones mentioned under the heading “Mixtures” to form synergistic mixtureswhere the mode of action of the compounds in the mixtures are the same,similar, or different.

Examples of mode of actions include, but are not limited to:acetylcholine esterase inhibitor; sodium channel modulator; chitinbiosynthesis inhibitor; GABA-gated chloride channel antagonist; GABA orglutamate-gated chloride channel agonist; acetylcholine receptoragonist; MET I inhibitor; Mg⁺-stimulated ATPase inhibitor; nicotinicacetylcholine receptor agonist or antagonist; Midgut membrane disrupter;and oxidative phosphorylation disrupter.

Additionally, the following compounds are known as synergists and can beused with the invention disclosed in this document: piperonyl butoxide,piprotal, propyl isome, sesamex, sesamolin, and sulfoxide.

Formulations

A pesticide is rarely suitable for application in its pure form. It isusually necessary to add other substances so that the pesticide can beused at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticide activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra low volume solutions.

For further information on formulation types see “CATALOGUE OF PESTICIDEFORMULATION TYPES AND INTERNATIONAL CODING SYSTEM” Technical Monographn°2, 5th Edition by CropLife International (2002).

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations, areeither solids, usually known as wettable powders, or water dispersiblegranules, or liquids usually known as emulsifiable concentrates, oraqueous suspensions. Wettable powders, which may be compacted to formwater dispersible granules, comprise an intimate mixture of thepesticide, a carrier, and surfactants. The concentration of thepesticide is usually from about 10% to about 90% by weight. The carrieris usually chosen from among the attapulgite clays, the montmorilloniteclays, the diatomaceous earths, or the purified silicates. Effectivesurfactants, comprising from about 0.5% to about 10% of the wettablepowder, are found among sulfonated lignins, condensednaphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates,alkyl sulfates, and nonionic surfactants such as ethylene oxide adductsof alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are chosen from conventionalanionic and nonionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums, may also be added, to increase the densityand viscosity of the aqueous carrier. It is often most effective togrind and mix the pesticide at the same time by preparing the aqueousmixture and homogenizing it in an implement such as a sand mill, ballmill, or piston-type homogenizer.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier which has beenpre-formed to the appropriate particle size, in the range of from about0.5 to 3 mm. Such compositions may also be formulated by making a doughor paste of the carrier and compound and crushing and drying to obtainthe desired granular particle size.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. They canbe applied as a seed dressing, or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. They are used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings or in special chambers.

Pesticides can be microencapsulated by suspending the pesticideparticles or droplets in plastic polymers of various types. By alteringthe chemistry of the polymer or by changing factors in the processing,microcapsules can be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which, inturn, affects the residual performance, speed of action, and odor of theproduct.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one compound which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers. Further information onthe embodiment is disclosed in U.S. patent publication 20070027034published Feb. 1, 2007, having patent application Ser. No. 11/495,228.For ease of use this embodiment will be referred to as “OIWE”.

For further information consult “INSECT PEST MANAGEMENT” 2nd Edition byD. Dent, copyright CAB International (2000). Additionally, for moredetailed information consult “HANDBOOK OF PEST CONTROL—THE BEHAVIOR,LIFE HISTORY, AND CONTROL OF HOUSEHOLD PESTS” by Arnold Mallis, 9thEdition, copyright 2004 by GIE Media Inc.

Other Formulation Components

Generally, the invention disclosed in this document when used in aformulation, such formulation can also contain other components. Thesecomponents include, but are not limited to, (this is a non-exhaustiveand non-mutually exclusive list) wetters, spreaders, stickers,penetrants, buffers, sequestering agents, drift reduction agents,compatibility agents, anti-foam agents, cleaning agents, andemulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulphate;sodium dioctyl sulphosuccinate; alkyl phenol ethoxylates; and aliphaticalcohol ethoxylates.

A dispersing agent is a substance which adsorbs onto the surface of aparticles and helps to preserve the state of dispersion of the particlesand prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulphonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such as sodium naphthalene sulphonate formaldehydecondensates. Tristyrylphenol ethoxylate phosphate esters are also used.Non-ionics such as alkylarylethylene oxide condensates and EO-PO blockcopolymers are sometimes combined with anionics as dispersing agents forsuspension concentrates, In recent years, new types of very highmolecular weight polymeric surfactants have been developed as dispersingagents. These have very long hydrophobic ‘backbones’ and a large numberof ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.These high molecular weight polymers can give very good long-termstability to suspension concentrates because the hydrophobic backboneshave many anchoring points onto the particle surfaces. Examples ofdispersing agents used in agrochemical formulations are: sodiumlignosulphonates; sodium naphthalene sulphonate formaldehydecondensates; tristyrylphenol ethoxylate phosphate esters; aliphaticalcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graftcopolymers.

An emulsifying agent is a substance which stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends containalkylphenol or aliphatic alcohol with 12 or more ethylene oxide unitsand the oil-soluble calcium salt of dodecylbenzene sulphonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from 8 to 18 willnormally provide good stable emulsions. Emulsion stability can sometimesbe improved by the addition of a small amount of an EO-PO blockcopolymer surfactant.

A solubilizing agent is a surfactant which will form micelles in waterat concentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilized water-insoluble materialsinside the hydrophobic part of the micelle. The type of surfactantsusually used for solubilization are non-ionics: sorbitan monooleates;sorbitan monooleate ethoxylates; and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alky ethoxylates; linear aliphatic alcoholethoxylates; aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersare usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, ULV formulations, and to a lesser extent granularformulations. Sometimes mixtures of solvents are used. The first maingroups of solvents are aliphatic paraffinic oils such as kerosene orrefined paraffins. The second main group and the most common comprisesthe aromatic solvents such as xylene and higher molecular weightfractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons areuseful as cosolvents to prevent crystallization of pesticides when theformulation is emulsified into water. Alcohols are sometimes used ascosolvents to increase solvent power.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, emulsions and suspoemulsions to modify therheology or flow properties of the liquid and to prevent separation andsettling of the dispersed particles or droplets. Thickening, gelling,and anti-settling agents generally fall into two categories, namelywater-insoluble particulates and water-soluble polymers. It is possibleto produce suspension concentrate formulations using clays and silicas.Examples of these types of materials, include, but are limited to,montmorillonite, e.g. bentonite; magnesium aluminum silicate; andattapulgite.

Water-soluble polysaccharides have been used as thickening-gellingagents for many years. The types of polysaccharides most commonly usedare natural extracts of seeds and seaweeds or are synthetic derivativesof cellulose. Examples of these types of materials include, but are notlimited to, guar gum; locust bean gum; carrageenam; alginates; methylcellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose(HEC). Other types of anti-settling agents are based on modifiedstarches, polyacrylates, polyvinyl alcohol and polyethylene oxide.Another good anti-settling agent is xanthan gum.

Microorganisms cause spoilage of formulated products. Thereforepreservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are limited to: propionic acid andits sodium salt; sorbic acid and its sodium or potassium salts; benzoicacid and its sodium salt; p-hydroxy benzoic acid sodium salt; methylp-hydroxy benzoate; and 1,2-benzisothiazalin-3-one (BIT).

The presence of surfactants, which lower interfacial tension, oftencauses water-based formulations to foam during mixing operations inproduction and in application through a spray tank. In order to reducethe tendency to foam, anti-foam agents are often added either during theproduction stage or before filling into bottles. Generally, there aretwo types of anti-foam agents, namely silicones and non-silicones.Silicones are usually aqueous emulsions of dimethyl polysiloxane whilethe non-silicone anti-foam agents are water-insoluble oils, such asoctanol and nonanol, or silica. In both cases, the function of theanti-foam agent is to displace the surfactant from the air-waterinterface.

For further information see “CHEMISTRY AND TECHNOLOGY OF AGROCHEMICALFORMULATIONS” edited by D. A. Knowles, copyright 1998 by Kluwer AcademicPublishers. Also see “INSECTICIDES IN AGRICULTURE ANDENVIRONMENT—RETROSPECTS AND PROSPECTS” by A. S. Perry, I. Yamamoto, I.Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.

Applications

The actual amount of pesticide to be applied to loci of pests isgenerally not critical and can readily be determined by those skilled inthe art. In general, concentrations from about 0.01 grams of pesticideper hectare to about 5000 grams of pesticide per hectare are expected toprovide good control.

The locus to which a pesticide is applied can be any locus inhabited bya pest, for example, vegetable crops, fruit and nut trees, grape vines,ornamental plants, domesticated animals, the interior or exteriorsurfaces of buildings, and the soil around buildings. Controlling pestsgenerally means that pest populations, activity, or both, are reduced ina locus. This can come about when: pest populations are repulsed from alocus; when pests are incapacitated, partially or completely,temporarily or permanently, in or around a locus; or pests areexterminated, in whole or in part, in or around a locus. Of course acombination of these results can occur. Generally, pest populations,activity, or both are desirably reduce more than fifty percent,preferably more than 90 percent, even more preferably more than 99percent.

Generally, with baits, the baits are placed in the ground where, forexample, termites can come into contact with the bait. Baits can also beapplied to a surface of a building, (horizontal, vertical, or slant,surface) where, for example, ants, termites, cockroaches, and flies, cancome into contact with the bait.

Because of the unique ability of the eggs of some pests to resistpesticides repeated applications may be desirable to control newlyemerged larvae.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying the pesticides to adifferent portion of the plant, or to a location where the root systemof a plant can uptake pesticides. For example, control of foliar-feedinginsects can be controlled by drip irrigation or furrow application, orby treating the seed before planting. Seed treatment can be applied toall types of seeds, including those from which plants geneticallytransformed to express specialized traits will germinate. Representativeexamples include those expressing proteins toxic to invertebrate pests,such as Bacillus thuringiensis or other insecticidal toxins, thoseexpressing herbicide resistance, such as “Roundup Ready” seed, or thosewith “stacked” foreign genes expressing insecticidal toxins, herbicideresistance, nutrition-enhancement and/or any other beneficial traits.Furthermore, such seed treatments with a compound or composition of thepresent application can further enhance the ability of a plant to betterwithstand stressful growing conditions. This results in a healthier,more vigorous plant, which can lead to higher yields at harvest time.

It should be readily apparent that the invention can be used with plantsgenetically transformed to express specialized traits, such as Bacillusthuringiensis or other insecticidal toxins, or those expressingherbicide resistance, or those with “stacked” foreign genes expressinginsecticidal toxins, herbicide resistance, nutrition-enhancement and/orany other beneficial traits. An example of such a use is spraying suchplants with the invention disclosed in this document.

The invention disclosed in this document is suitable for controllingendoparasites and ectoparasites in the veterinary medicine sector or inthe field of animal keeping. Compounds according to the presentapplication are applied in a known manner, such as by oraladministration in the form of, for example, tablets, capsules, drinks,granules, by dermal application in the form of, for example, dipping,spraying, pouring on, spotting on, and dusting, and by parenteraladministration in the form of, for example, an injection.

The invention disclosed in this document can also be employedadvantageously in livestock keeping, for example, cattle, sheep, pigs,chickens, and geese. Suitable formulations are administered orally tothe animals with the drinking water or feed. The dosages andformulations that are suitable depend on the species.

Before a pesticide can be used or sold commercially, such pesticideundergoes lengthy evaluation processes by various governmentalauthorities (local, regional, state, national, international).Voluminous data requirements are specified by regulatory authorities andmust be addressed through data generation and submission by the productregistrant or by another on the product registrant's behalf. Thesegovernmental authorities then review such data and if a determination ofsafety is concluded, provide the potential user or seller with productregistration approval. Thereafter, in that locality where the productregistration is granted and supported, such user or seller may use orsell such pesticide.

The headings in this document are for convenience only and must not beused to interpret any portion thereof. All lists herein are inclusive ofany and all combinations of two or more members of the list and allranges are inclusive of any and all subsets within the range havingendpoints within the range as if each combination and subset wereexpressly stated herein. Unless stated otherwise or recognized by thoseskilled in the art as otherwise impossible, steps of processes describedherein are optionally carried out in sequences different from thesequence in which the steps are discussed herein. Furthermore, stepsoptionally occur separately, simultaneously or with overlap in timing.For instance, such steps as heating and admixing are often separate,simultaneous, or partially overlapping in time in the art. Unless statedotherwise, when an element, material, or step capable of causingundesirable effects is present in amounts or in a form such that it doesnot cause the effect to an unacceptable degree it is consideredsubstantially absent for the practice of this invention.

What is claimed is:
 1. A compound according to the

wherein A1, A2 and A3 are each C; X is N; Y is C; T is O; Z is C(R6)₂(where R6 could be the same or different); n=2; R1 is F, Cl, Br or I; R2is CN; R3 is a substituted or unsubstituted halo-C1-C4-alkyl; R4 is H;R5 is H; and R6 is chosen from H, substituted or unsubstituted C1-C4alkyl, and substituted or unsubstituted aryl.
 2. A compound accordingclaim 1, wherein R1 is Cl.
 3. A compound according to claim 2, whereinR3 is trifluoromethyl.
 4. A compound according to claim 3, wherein R6 ischosen from H, methyl, ethyl, propyl and benzyl.
 5. A method ofcontrolling insects which comprises applying to a locus where control isdesired an insect-inactivating amount of a compound according toclaim
 1. 6. A composition, comprising a compound according to claim 1and at least one other pesticide.
 7. A composition, comprising acompound according to claim 1 and at least one herbicide, at least onefungicide, or at least one herbicide and one fungicide.
 8. A compoundaccording to claim 1 having the following structure


9. A compound according to claim 1 having the following structure


10. A compound according to claim 1 having the following structure


11. A compound according to claim 1 having the following structure


12. A compound according to claim 1 having the following structure